Water insoluble monoazo dyestuffs



United States Patent U.S. Cl. 260207.1 4 Claims ABSTRACT OF THE DISCLOSURE There are disclosed herein water insoluble monoazo dyestuffs of the general formula SOZCHQ X I (321140 C 0 CH and method for making same comprising the step of coupling equimolar amounts of diazotized 1-amino-4-mtrobenZene-2-methylsulfone and C2H4O C O C H;

C2H40 C 0 CH3 wherein X is Cl, Br or CH Use of the dyes for dyeing synthetic linear polyester textile fibers, such as polyethylene terephthalate, in red range shades of outstanding fastness is also disclosed.

The present invention relates to dyestuffs, and more particularly to water insoluble monoazo dyestuffs and method for making same.

The dyestuffs 0f the present invention are particularly characterized in that they have the general formula SOZCHQ X C2H4O CO CH (I) wherein X is Cl, Br or CH Generally speaking, the method of the present invention is a method for preparing a water insoluble monoazo dyestuff of the above Formula I comprising the step of coupling equimolar amounts of diazotized 1-amino-4- nitrobenzene-Z-methylsulfone and CzHlO CO CH:

wherein X is Cl, Br or CH The dyestuffs of the present invention are particularly suitable for dyeing synthetic linear polyester textile fibers, such as polyethylene terephthalate, in red range shades of outstanding fastness properties by the known thermosol and carrier dyeing methods. In addition, the dyes of the present invention may be applied to polyamide and secondary cellulose acetate textile fibers. The dyes of Examples l and 3 below are also suitable for pigment dyeing of polystyrene film.

In recent years, very large amounts of synthetic linear polyester textile fibers have been blended with cotton fibers, and formed into fabric, the fabric dyed and then subjected to permanent press resin finish treatment, by processes which involve resinating the dyed fabric and delaying completely curing or polymerizing the resin precondensate until after garments have been fabricated and creased. That process (US. Patent No. 2,974,432) is commonly known as permanent press finishing. Permanent 3,497,495 Patented Feb. 24, 1970 SIO CH;

C2H4O C 0 CH (II) CzHAO C 0 CH3 for dyeing acetate artificial silk. I have found that one important difficulty with this red dye of Formula II for dyeing synthetic linear polyester textile fibers is that when it is applied thereto by the conventional long bath carrier method it will not build up to heavy shades, which is to say that it has poor shade building properties or less than desirable aflinity for synthetic linear polyester textile fibers when applied by the commonly used long bath carrier dyeing method. Other important difiiculties are that when the dye of Formula II is applied to cotton/synthetic linear polyester blends and the dyeing subjected to permanent press finishing with dimethylol dihydroxy ethylene urea resin, the light fastness and wash fastness of the dye are substantially impaired.

British patent specification 1,047,229 discloses generally the dye of the formula sozorn H3 C2H4O C 0 CH3 (III) for use on linear polyester materials. The primary difficulty with this Bordeaux (somewhat violet) dye is that it has less than desirable light fastness when applied to blended cotton/ synthetic linear polyester textile fabric and the dyeing subjected to permanent press finishing with dimethylol dihydroxy ethylene urea resin.

Although there are a number of red dyes for synthetic linear polyester textile fibers present on the market, all of them with which I am familiar are deficient in one or more desirable properties.

According to the present invention, the above disadvantages and limitations of the prior art have been overcome, and additional advantages have been provided as follows.

The dyes of the present invention are particularly suitable for dyeing synthetic linear polyester textile fibers, ineluding dyeing the polyester portion of cotton/polyester blends which may optionally be after-treated by permanent press finishing. The fastness properties of the dyes of the present invention are outstanding, as shown in detail hereinafter. Moreover, they have good to very good shade building power from light to heavy shades when applied by the long bath carrier dyeing method. Moreover, the dyestutf of Example 1 below is the best all around red dye for synthetic linear polyester textile fibers with which I am familiar.

The following is a more detailed description for preparing the dyes of the present invention. All parts herein are by weight unless otherwise specified.

1-amino-4-nitrobenzene-2-methylsulfone (Chem. Ab., 27:4685 may be diazotized with nitrosylsulfuric acid (US. Patent 2,118,661) and acetic acid.

Nitrosylsulfuric acid may be prepared by adding 1 part NaNOg to 10 parts 96% H 80 heating at about -85 C. for about 10 minutes, and cooling to 15-18 C.

The diazotization step may be conducted by adding 4.8

parts glacial acetic acid at 1518 C. to 6 parts nitrosylsulfuric acid at 15-18 C., and adding 1 part l-amino- 4-nitrobenzene-2-methylsulfone thereto at 15 18 C., and stirring about 3 hours at 20" C., and preferably at 15- 18 C., to produce a solution of diazotized 1-amino-4- nitrobenzene-Z-methylsulfone. The diazo may be diluted by adding it at 15 -18 C. to a mixture of 30 parts H 0 and parts ice, following which 0.08 part sulfamic acid may be added to remove excess nitrous acid.

An acetic anhydride solution of CHrCH2'OfJCH 0 (IV) may be prepared by heating 1 part acetic anhydride to 113-115 C., adding 1 part I /CH2-CHr-OH CHz-GHz-OH at 113115C., stirring 1 hour at 113-115 C., and cooling to room temperature, in which X is as above defined.

The coupling reaction may be conducted as follows. To 1 part of the acetic anhydride solution of a compound of Formula IV above at room temperature may be added 1 part H O, 2-3 parts 1:5 acid (1 part propionic acid to 5 parts glacial acetic acid), 0.8 part sodium acetate and 0.2 part sodium lignosulfonate dispersing agent, and the composition cooled to about 0l0 C. The above diazotized [and diluted 1 amino-4-nitrobenzene-2-methylsulfone, in equimolar amount to the amount of the compound of Formula I'V used, calculated as solids, may be added to the coupling component at about 0l0 C., gradually over a period of about an hour, simultaneously with addition of about 3-4 parts 30% aqueous sodium acetate, and 34 parts 1:5 acid, while the reaction mixture is maintained at about 0l0 C. The reaction mixture may be stirred at about 0 -10 C. for about 2 hours, following which coupling is complete.

The resulting dyestuif may be recovered by drowning in a large volume of water containing about 1% sodium lignosulfonate, recovering the dyestuif solids by filtration, and washing the solids with water at tap tem perature until free of acids. The dyestuif solids may be Worked up from the moist presscake or dried at about 40 C. If desired, the dyestuff solids may be recrystallized from an ethanol solution thereof to remove any impurities.

The following are illustrative examples.

EXAMPLE 1 The dyestuff of the formula OzN- may be prepared as follows.

1 amino-4-nitrobenzene-2-methylsulfone (Chem. Ab, 27 :4685 is diazotized as follows. Nitrosylsulf-uric acid is prepared by adding 4.8 gms. NaNO- to 48 ml. 96% H 80 holding minutes at 70-80 C. and cooling to 18 C. Sixty ml. glacial acetic acid at -18 C. is added to the nitrosylsulfuric acid, and 13.1 gms. l-amino-4-nitrobenzene-2-methylsulfone is then added thereto at 15-18 C., the mixture is stirred 3 hours at 15 -18 C. to produce a solution of diazotized l-amino- 4-nitrobenzene-2-methylsulfone, which is diluted by adding the diazo at 15-18 C. to a mixture of 400 ml. H 0 and 64 gms. ice, following which 1 gm. of sulfamic acid is added to remove excess nitrous acid.

An acetic anhydride solution of N,,8,N,,8-diacetoxyethyl-m-chloroaniline is prepared as follows. gms. ace-tic anhydride is heated to C., 100 gms. 2,2-(-mchlorophenylimino)diethanol (US. Patent No. 2,618,- 613) is added thereto at 113-115 C., and held with stirring 1 hour at 115 C., followed by cooling to room temperature.

The above components are coupled as follows.

To 35.2 gms. of the acetic anhydride solution of N, 8,N,p-diacetoxyethylm-chloroaniline are added 40 ml. H 0, 102 gms. of a mixture of 17 gms. propionic acid and 85 gms. glacial acetic acid, 28 gms. sodium acetate, and 8 gms. sodium lignosulfonate dispersing agent, which is cooled to 5-10 C. The above diluted solution of diazotized 1-amino-4-ni-trobenzene-2-methylsulfone is added thereto gradually during a period of 1 hr., while the reaction mixture is maintained at 5-10 C. Simultaneously with the addition of the diazo there is added ml. 30% aqueous sodium acetate, and 120 gms. of a mixture of 20 gms. propionic acid and 100 gms. glacial acetic acid. The reaction mixture is stirred at 5-10 C. for 2 additional hours, following which coupling is complete. The resulting mass is drowned in 1.2 liters H O containing 12 gms. sodium lignosulfonate, and the dyestuff solids are recovered by filtration, washed with tap water until free of acids, and dried at 40 C. If desired, the dyestuif may be recrystallized from an ethanol solution thereof to remove any impurities.

EXAMPLE 2 The dyestuif of the formula OzN EXAMPLE 3 The dyestuif of the formula S 020113 B! l CHz-CHz-O-C-CHa (VII) may be prepared as follows.

This example is the same as Example 1 above, except that 100 gms. 2,2'-(m-bromophenylimino)diethanol (US. Patent No. 2,618,631) is substituted for the 100 gms. 2,2- (2-chlorophenylimino)diethanol of Example 1 to produce an acetic anhydride solution of N,,8,N,/3-diacetoxyethyl-m-bromoaniline, and except that 41.2 gms. of the acetic anhydride solution of N,fl,N,B-diacetoxyethyl-mresults are presented in Table A below. Pattern and stain bromoaniline is substituted for the 35.2 gms. acetic anreadings are on the Grey Scale in which 5 is optimum.

TABLE A Test Formula II Dye Formula III Dye Formula V Dye Formula VI Dye Formula VII Dye Shade Dull red Bordeaux Red Rubine Brick red. Light fastness light shade More than 60 hours Slight break at 40 More than 60 hours More than 60 hours More than 60 hours without break. hours. without break. without break. without break. Light fastness heavy shade "do .do do d ..Do. Wash fastness light shade Excellent; Pattern 4-5 Excellent; Pattern 5 Excellent; Pattern 4-5 Excellent; Pattern Excellent; Pattern 5,

Stain 5. Stain 5. Stain 5. Stain 5. Stain 5. Wash fastness heavy shade Very good; Pattern 4, Excellent; Pattern 5, Very good; Pattern 4, do Do.

tain 4-5. Stain 4-5. Stain 4-5. siibliniat'ioriglit shade Excellent; Stain 5.- Excellent Stain 5 Excellent; Stain 5 Excellent; Stain 5 Excellent; Stain 5.

minu e Sublimation heavy shade .do Good; Stain 4 do Very good; Stain 4-5 Good; Stain 4.

1 minute 400 F.

hydride solution of N,B,N,fl-diacetoxyethyl-m-chloroani- The dyes of Formulas II, III, V, VI and VII above were line used in Example 1. next applied to woven blended textile fabric consisting of The following relates to dispersing and applying the 65% polyethylene terephthalate and 35% cotton by the dyes of the present invention (Formulas V-VII) to syndyeing method described for the dyeings listed in Table thetic linear polyester and to comparing these dyeings A, except that the cotton portion of the fibers were not disagainst similar dyeings made from the dyes of Formulas solved, and except that residual surface dye was cleared II and III. i by immersing the dyeings for 10 minutes in 56.8 gins.

Each of the dyes of Formulas II, III, V, VI and VII NaOH and 56.8 gms. Na S O per gallon of water at above was dispersed by charging into a ball mill 15 parts 140 F., rinsing with water, soaping, rinsing and drying;

dried dye, 10.2 parts sodium lignosulfonate, 10.2 parts 113.6 gms. 15% aqueous dispersions of the dyes were glycerine and 54 parts water. The compositions were ball used. Portions of the dyeings were then subjected to the milled until the dye particles were substantially uniform following tests; carbon are light fastness, No. 3 AATCC and averaged 1-2 microns. Enough water was added to wash fastness, sublimation fastness, gas (oxides of nitroeach to bring its final volume to 100 parts, resulting in a gen) fastness, and ozone fastness, and the results are given 15% aqueous dispersion of each dye. in Table B below.

Light and heavy shades dyeings of each of the dyes of Other portions of the cotton/ polyester dyeings were re- Formulas II, III, V, VI and VII above were made on served and subjected to permanent press resin finishing in woven blended 65% polyethylene terephthalate/ cotthe known manner (U.S. Patent No. 2,974,432) using diton textile fabric samples as follows. The light shades dyemethylol dihydroxy ethylene urea resin, and the perings were made by mixing padding liquors containing manent press finished fabric was then subjected to the 56.8 gins. 15% aqueous dye dispersion, 113.6 gms. so- 35 tests and observations recorded in Table C below.

TABLE B Test Formula II Dye Formula III Dye Formula V Dye Formula VI Dye Formula VII Dye Shade Dull red Bordeaux Red Rubine Brick red. Light fastness Trace break hours.. Trace break 20 hours.. More than hours More than 60 hours Trace break 40 hour without break. without break. Wash fastness Ecxellent; Pattern 4-5 Excellent; Pattern 5, Excellent; Pattern 5, Excellent; Pattern 5, Excellent; Pattern 5,

Stain 5. Stain 5. Stain 5. Stain 5. Stain 5. Sublimation 1 minute 400 F. Excellent; Stain 5 Very good; Stain 4-5" Excellent; Stain 5-.-.. Very good; Stain 4-5 Excellent; Stain 5. Gas fastness Excellent Excellent Excellent Excellent Excellent. Ozone fastness ..d0 d0 Do.

TABLE 0 Test Formula II Dye Formula III Dye Formula V Dye Formula VI Dye Formula VII Dye Shade Dull red Red Rubiue Brick red. Shade change on permanent Moderate Very slight Very slight Very slight.

. fl hi rigii t iasi fiss f Break at 20 hours. Break at 20 hours- More than 60 hours. Slight break at 60 Trace break at 20 without break. hours hours and 40 hours. No. 3 AATCC wash fastness Fair; Pattern 3-4, Very good; Pattern Excellent; Pattern 5, Very good; Pattern 4-5, Very good; Pattern 4-5.

test. S ain 3. 4-5, Stain 4. Stain 5. Stain 4. Stain 4-5. Sublimation 1 minute at Excellent; Stain 5--. Very good; Stain 4-5. Excellent; Stain 5. Very good; Stain 45 Excellent; Stain 5.

G3 fastness Excellent Excellent Excellent Excellent Excellent. Ozone fastness do 0 "do d0 Do.

dium alginate migration inhibitor, and enough water to The following tests relate to comparing the shade buildbring to 1 gallon; the fabric was padded through the liquor 0 ing power of the dyes of Formulas II, IH, V, VI and VII. at room temperature; squeezed with nip rollers to 60% wet These dyes were applied to polyethylene terephthalpickup based on fabric weight; predried to substantial dryate/ 35% cotton textile fabric by the conventional long ness; the dyes were fixed by exposing the fabric to dry bath carrier dyeing method, using emulsified o-phenylpheheat in an oven at 415 F. for 90 seconds; whereafter the 1101 carrier. The amounts of each dye were progressively fabrics were scoured and dried. The heavy shades dyeings 5 varied so that dyeings of 0.5%, 1%, 2% and 4% were made in similar manner, except that the amounts of strength were prepared. In this method, the liquor to 15% aqueous dye dispersion were increased in each ingoods ratio was 30:1 and relates to weight of 15% stance to 113.6 gms. The cotton portion of the fabric was dye dispersion (calculated as dispersion) in the dye then dissolved and removed from the fabric by treating liquor t i ht of f b i the fabric with aqueous H 80 rinsing with water, 70 It was observed that the dyes of Formulas II, III, V, neutralizing with ammonia and drying. VI and VII built equally well to medium depths of shade,

The dyeings, having only the polyester portion of the and that all of the dyes, except the dye of Formula II, fibers remaining, were then subjected to light fastness built to moderately heavy and heavy shades; the dye of tests in the Fade-Ometerfib carbon arc light fastness tester, Formula II did not build to moderately heavy or heavy No. 3 AATCC wash tests, and sublimation tests and the depths of shade.

3,497,495 7 8 What is claimed is: References Cited 1. A water insoluble monoazo dyestufit of the formula UNITED STATES PATENTS 302C113 X if 2,082,156 6/1937 Felix et al. 260207.5 X

OHPCHPO C CH3 1,047,229 Great Britain.

0 CHARLES B. PARKER, Primary Examiner wherein X is Cl, Br or CH 2. A dyestufif as defined in claim 1, and further char- 10 CHARLES WARREN Assistant Examiner acterized in that X is Cl.

3. A dyestuff as defined in claim 1, and further characterized in that X is Br.

4. A dyestufl? as defined in claim 1, and further charac- 15 terized in that X is CH UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,497,495 February 24, 1970 'Duncan G. Carmichael It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 43, "present" should read presently Column 4, line 73, "(Z-chlorophenylimino)diethanol" should read (m-chlorophenylimino)diethanol Columns 5 and 6, TABLE A,

fifth column, line 5 thereof, "Excellent; Pattern" should read Excellent; Pattern 5 Signed and sealed this 1st day of December 1970.

(SEAL) Attcst:

Edward M. Fletcher, Jr. E. J

Attesting Officer Commissioner of Patents 

